Process for resolving emulsions using azolidine salts of alkylated naphthalene sulfonic acids



OFFICE PRGCESS FOR RESOLVING EMULSIONS USING AZOLIDINE SALTS OF ALKYL- ATED NAPHTHALENE SULFONIC ACIDS William B. Hughes, Bartlesville, Okla., assignor to Cities Service Oil Company, Bartlesville, Okla, a corporation of Delaware No Drawing. Application January 31, 1950, Serial No. 141,598

8 Claims. (Cl. 252-338) This invention relates to surface active com- Patent No. 1,873,165. The compound has the pounds, and more particularly to compounds efformula: fective to cause a rapid and complete separation of the oil and water phases of a water-in-oil emulsion. 5 SOSH (2)" One of the most troublesome problems met with in crude oil production relates to the breaking of water-in-oil emulsions formed in wells producing both oil and brine. Unless these emulm Whlch Z 15 an lsopropyl radlcal, and n is sions can be rapidly and completely broken, their Whole number: from 1 oil content is lost. These emulsions will vary in Generally preparlllg my new demu11fiers' properties from well to well and even from day I Prefer to mm t amme and aldehyde m to day in the same well, so that it may be necesproxlmately equlmolar proportmns, and then Sary to use one demulsifier on one well, and heat the mixture to force the reaction to comanother on an adjacent well, in Order to secure pletion and to drive the water formed in the optimum results. reaction overhead. The reaction will proceed It is an object of this invention to provide a in accordance with the following general equaseries of compounds effective to rapidly resolve water-in-oil emulsions of the type commonly met with in crude oil production, to permit a complete H (CEmFCm recovery of the oil content of the emulsion. C= N I H1O It has been found that azolidines formed by H ()5 the reaction of an aldehyde with a primary or secondary alkanol amine, neutralized with a propylated naphthalene sulfonic acid, are effective in breaking a Wide variety of wate -oil R being an alkanol radical or a hydrogen atom, emulsions. These compositions will vary someand R being an alkyl radical or a hydrogen atom. wh in pr p r depending p n h partic lar The product is then neutralized to a methyl aldehyde or amine chosen as the starting maorange end point with propylated naphthalene terial, so that it is possible, by proper selection sulfonic acid to give a product having the folof the aldehyde or amine, to tailor the composition to fit the individual emulsion which it is desired to break.

Among aldehydes which are suitable as starting materials for my new compositions may be men- (2)" tioned formaldehyde, acetaldehyde, propionallowing generic formula:

dehyde, butyraldehyde, and higher aldehydes. I

prefer, however, to use heptaldehyde, since I Q: /(CHI)v-CH1 have found that the higher aldehydes give gen- RN erally better results, and heptaldehyde is availag O ble commercially at a reasonable cost. Aldehydes higher than heptaldehyde may also be used, but are not preferred since their cost at the present time is such as to render them commercially unattractive.

As the amine, I prefer to use monoethanol amine or diethanol amine, since these amines are available commercially at low cost. Other alkanol amines, such as the propanol and butanol in which Z is an isopropyl radical, and n is a whole number from 1 to 4.

In order that those skilled in the art may more fully appreciate the nature of my invention and the manner of carrying it out, the following example is given,

amines, and higher alkanol amines, may also be Example used. Heptaldehyde and diethanol amine were mixed Th p py naphthalene Sulfonlc aflld in the proportion of 114 grams of heptaldehyde which I use as the neutr z agent for y and grams of diethanol amine. The mixture termediate compounds may be prepared accordwas then heated at a temperature of about ing to the directions given by Walker in U. S. 55 C. until water ceased to evolve, the time necessary being about one hour, to yield a product having the formula This product was then neutralized to a methyl orange end point with propylated naphthalene sulfonic acid.

The neutralized product may be used with success as a demulsifler in relatively pure form, but since it is rather viscous, and is di-iiicult to inject into gathering lines during cold weather, it may be diluted to the desired viscosity with crude oil, other suitable hydrocarbon fractions, or other suitable solvents such as dichlorodiethyl ether, chloronaphthalene, ketones, or alcohols in amounts ranging from about 10 to about 60 per cent of the total mixture. The product may also be used in combination with other commercial demulsifiers in order to improve their characteristics.

The various compositions described above are effective to break'a'vvide varietyof emulsions, and are low in cost. While they are not uniformly successful in completely resolving every em.ulsion encountered in the oil fields, they may be advantageously utilized as an ingredient of a composite demulsifier "which will resolve emulsions which the present compositions are incapable of completely resolving. For example, an emulsion which they are capable of breaking completely, but on which they show poor water separation action, may successfully be treated by adding to the composition from about 1 per cent to about 10 per cent of the water separation agents disclosed in my copending application Serial No. 141,597 filed concurrently herewith.

Having now described my invention, What is claimed as new and useful is:

l. The process of resolving emulsions including subjecting a petroleum water-in-oil emulsion to the action of a compound having the generic formula in which Z is an isopropyl radical, n is a whole number from 1 to 4, y is a whole number less than 4, R is a member of the class consisting of sion to the action of a compound according to claim 1 in which R is a hydrogen atom and y is 1.

4. The process of resolving emulsions including subjecting a petroleum water-in-oil emulsion to the action'o'f a compound according to claim 1 in which R" is a hexyl radical.

.5. Theprocess of resolving emulsions including subjecting a petroleum water-in-oil emulsion to the action of a compound according to claim 1 in which R is a hexyl radical, R is an ethanol radical, and y is 1.

t. The process of resolving emulsions including subiecting a petroleum waiter-imo'il emu-l sion to the action of -a compound according to claim 1 in which R" is a hexyl radical, R is 'a hydrogen atom, and y is l.

'7. A demulsifying composition consisting essential'ly of from about 40 to about '91) par-ts by weight of a compound having the generic formula in which Z is an isopropyl radical, R is a member of the class consisting of alltanol radicals and hydrogen atoms, R is a member of the class consisting of alkyl radicals and hydrogen atoms, n is a Whole number from 1 to 4, and .y is a whole number less than 4; and from about 69 to about 10 parts by weight of a solvent selected from the group consisting of hydrocarbons, chlorinated hydrocarbons, ethers, ketones, and alcohols.

8. The composition according to claim l in which the solvent is a hydrocarbon fraction.

WILLIAM 'B. HUGHES.

References Cited in the file of this patent STATES PATENTS Number Name Date 2,11'0537 Blair Mar. 8, 1938 12,226,118 De Groote Dec. 24,1940 2,352,152 Kapl'an June 20, T944 

1. THE PROCESS OF RESOLVING EMULSIONS INCLUDING SUBJECTING A PETROLEUM WATER-IN-OIL EMULSION TO THE ACTION OF A COMPOUND HAVING THE GENERIC FORMULA 